CN110746356A - Preparation method and application of difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure - Google Patents
Preparation method and application of difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure Download PDFInfo
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- CN110746356A CN110746356A CN201911191865.XA CN201911191865A CN110746356A CN 110746356 A CN110746356 A CN 110746356A CN 201911191865 A CN201911191865 A CN 201911191865A CN 110746356 A CN110746356 A CN 110746356A
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- trifluoromethyl
- chloropyrazole
- oxime ester
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- pyrazole oxime
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
Abstract
The invention relates to a preparation method and application of difluoromethyl pyrazole oxime ester (I) containing a 3-trifluoromethyl-5-chloropyrazole structure. Obtained by reacting difluoromethylpyrazole oxime (II) with 3-trifluoromethylpyrazolecarbonyl chloride (III). The difluoromethyl pyrazole oxime ester containing the 3-trifluoromethyl-5-chloropyrazole structure has an effective control effect on harmful insects, and the compound can be used for preparing insecticides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, in particular to a preparation method and application of difluoromethyl pyrazole oxime ester containing a 3-trifluoromethyl-5-chloropyrazole structure.
Background
The prevention and control of pests are always the core field of pesticide science research, and the wide use of pesticides enables most pests to be effectively treated. However, with the continuous expansion of the application scale of the pesticide, the problem of drug resistance of the traditional pesticide varieties becomes more and more prominent, and the continuous research and development of new pesticides become necessary choices due to the continuous emergence of new plant diseases and insect pests.
Pyrazole oxime compounds are important nitrogen-containing heterocyclic compounds and play an important role in agriculture, and a representative compound is fenpyroximate.
The substituted pyrazole ring is also an important nitrogen-containing heterocyclic unit, and the pyrazole compound also has a wide insecticidal effect, such as a novel pyrazole insecticide chlorantraniliprole, has the advantages of broad spectrum, long lasting period, environmental friendliness and the like, and particularly has an excellent control effect on lepidoptera pests such as diamondback moth and the like.
Therefore, in order to further search for a compound with good biological activity from pyrazole oxime, a pyrazole unit and a pyrazole oxime mother nucleus are connected together, and the invention discloses difluoromethyl pyrazole oxime ester containing a 3-trifluoromethyl-5-chloropyrazole structure, which has agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide difluoromethyl pyrazole oxime ester containing a 3-trifluoromethyl-5-chloropyrazole structure, which has good control effect on harmful insects, is efficient, safe and environment-friendly, and meets the requirement of crop protection on high-efficiency insecticides.
It is a further object of the present invention to provide the use of the above compounds in the preparation of insecticides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
In order to solve the technical problems, the invention provides a difluoromethyl pyrazole oxime ester containing a 3-trifluoromethyl-5-chloropyrazole structure, which has a structure shown in a general formula I,
preferably, the difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure has the following structure:
the second aspect of the present invention provides a preparation method of the difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure, which comprises the following steps:
dissolving a compound II in an organic solvent, adding an acid-binding agent, dropwise adding a mixed solution of the intermediate III and a small amount of solvent, reacting for a period of time after dropwise adding, concentrating mother liquor under reduced pressure, separating and purifying an obtained crude product to obtain a target compound I,
preferably, the preparation method of the difluoromethyl pyrazole oxime ester containing the 3-trifluoromethyl-5-chloropyrazole structure comprises the following steps:
wherein, the synthesis of the difluoromethyl pyrazole oxime intermediate refers to the conventional method reported in the literature (J.Agric.FoodChem.2008,56, 10805-10810); the synthesis of trifluoromethyl pyrazole carbonyl chloride intermediates is described in the literature by conventional methods (organic chemistry, 2011,31, 1943-.
The compound of the general formula I shows good control effect on insects, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture and the like. The insects include armyworms and the like. Of course, the pests which the compounds of the invention can control are not limited to the above exemplified ranges.
When the compound of the invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, the compound can be used alone or in the form of an insecticidal composition, for example, the compound is prepared into an aqueous emulsion, a suspending agent, a water dispersible granule, an emulsion and the like by taking the formula I as an active ingredient and adding pesticide auxiliaries commonly used in the field.
Commonly used pesticide adjuvants include liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; common surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention represented by the general formula I is used as an active ingredient in an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the suspension concentrate contains 5% to 50% of active ingredient, preferably 5% to 40%.
For the use of the insecticide of the present invention, a commonly used application method such as stem and leaf spraying, water surface application, soil treatment, seed treatment, and the like can be selected. For example, when spray application from stems and leaves is employed, the compounds represented by the general formula I as active ingredients can be used in the form of aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates in the concentration range of 1 to 1000. mu.g/mL, preferably in the concentration range of 1 to 500. mu.g/mL.
The difluoromethyl pyrazole oxime ester containing the 3-trifluoromethyl-5-chloropyrazole structure disclosed by the invention has good insecticidal activity on harmful insects, so that the difluoromethyl pyrazole oxime ester can be used for preparing insecticides used in the fields of agriculture, horticulture and the like.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1:
a reaction flask was charged with 3mmol IIa, 20mmol triethylamine and 30mL dichloromethane. While stirring in an ice bath, a mixture of 6mmol of III and 3mL of dichloromethane was added dropwise thereto. After the completion of the dropwise addition, stirring was continued at room temperature for 13 hours. After the solvent is removed, the obtained residue is separated by column chromatography to obtain a target compound Ia;1H NMR(400MHz,CDCl3)δ:8.08(s,1H,CH＝N),6.80～7.24(m,5H,Ar-H and CHF2),3.94(s,3H,CH3),3.84(s,3H,CH3).
example 2:
a reaction flask was charged with 4mmol IIb, 30mmol sodium acetate and 20mL chloroform. While stirring in an ice bath, a mixture of 6mmol of III and 3mL of chloroform was added thereto. After the addition, the reaction was stirred at room temperature for 18 hours. After removal of the solvent, the residue obtained isSeparating by column chromatography to obtain target compound Ib;1H NMR(400MHz,CDCl3)δ:8.18(s,1H,CH＝N),7.31～7.37(m,1H,Ar-H),6.74～7.07(m,4H,Ar-H and CHF2),3.94(s,3H,CH3),3.77(s,3H,CH3).
example 3:
a reaction flask was charged with 5mmol IIc, 20mmol 4-Dimethylaminopyridine (DMAP) and 30mL acetone. To this was added a mixed solution of 7mmol of intermediate III and 6mL of acetone with stirring at room temperature. After the addition, the reaction was continued under heating and reflux for 20 hours. Removing the solvent under reduced pressure, and separating the obtained residue by column chromatography to obtain a target compound Ic;1H NMR(400MHz,CDCl3)δ:8.11(s,1H,CH＝N),6.79～7.09(m,5H,Ar-H and CHF2),3.94(s,3H,CH3),3.79(s,3H,CH3).
example 4:
a reaction flask was charged with 5mmol IId, 35mmol pyridine and 30mL DMF. A mixture of 5mmol of III and 5mL of DMF was added thereto with stirring in an ice bath. After the addition, the mixture was heated to 80 ℃ and reacted for 16 hours. After the solvent is removed, the obtained residue is separated by column chromatography to obtain a target object Id;1H NMR(400MHz,CDCl3)δ:8.19(s,1H,CH＝N),7.29～7.33(m,1H,Ar-H),7.15～7.18(m,1H,Ar-H),6.80～7.07(m,3H,Ar-H and CHF2),3.94(s,3H,CH3),3.77(s,3H,CH3).
example 5:
a reaction flask was charged with 8mmol IIe, 30mmol triethylamine and 30mL tetrahydrofuran. While stirring in an ice bath, a mixture of 7mmol of III and 6mL of tetrahydrofuran was added thereto. After the addition, the ice bath is continued to stirStirring and reacting for 12 hours. Removing the solvent, and separating the obtained residue by column chromatography to obtain a target compound Ie;1H NMR(400MHz,CDCl3)δ:8.17(s,1H,CH＝N),7.48(d,J＝8.8Hz,2H,Ar-H),6.77～7.04(m,3H,Ar-H and CHF2),3.94(s,3H,CH3),3.77(s,3H,CH3).
example 6:
a reaction flask was charged with 6mmol IIf, 20mmol sodium carbonate and 30mL acetonitrile. To this was added a mixture of 8mmol of III and 6mL of acetonitrile with stirring in an ice bath. After the addition, the reaction was heated under reflux for 15 hours. Removing the solvent, and separating the obtained residue by column chromatography to obtain a target compound If;1H NMR(400MHz,CDCl3)δ:8.18(s,1H,CH＝N),7.67(d,J＝8.8Hz,2H,Ar-H),6.76～7.05(m,3H,Ar-H and CHF2),3.94(s,3H,CH3),3.76(s,3H,CH3).
example 7:
insecticidal activity screening of samples against armyworm
The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the target for testing is armyworm, namely, a proper amount of corn leaves are fully soaked in prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed into a culture dish filled with filter paper, 10 heads/dish of armyworm larvae in the 3-instar middle stage are connected, the corn leaves are placed into an observation room for culture at 24-27 ℃, and the result is investigated after 2 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The assay concentration was 500. mu.g/mL.
Example 8:
screening of insecticidal Activity of samples against aphids
The spray method proposed by the International Resistance Action Committee (IRAC) was used: the test target is aphid, namely broad bean leaves connected with the aphid are sprayed under a Potter spray tower, the processed aphid is cultured in an observation room at 20-22 ℃, and the result is investigated after 2 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration is 500. mu.g/mL (other concentrations of the drug solution can be obtained by diluting 500. mu.g/mL of the drug solution).
The insecticidal activity test shows that (table 1), when the concentration is 500 mug/mL, the compounds Ia-if have good insecticidal action on armyworms, and the insecticidal activity is respectively 100%, 100%, 100%, 100%, 100% and 100%; in addition, the compound if has good insecticidal action on aphids at the concentration of 500 mu g/mL, and the insecticidal activity of the compound if reaches 100%.
TABLE 1 preliminary insecticidal Activity data for Ia-If
"-" means not determined
The experimental data show that the novel compound obtained by combining the trifluoromethyl pyrazole group and the pyrazole oxime skeleton has good insecticidal activity.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. Difluoromethyl pyrazole oxime ester I containing a 3-trifluoromethyl-5-chloropyrazole structure is characterized by having the following structure:
2. a process for preparing difluoromethyl pyrazole oxime ester I containing 3-trifluoromethyl-5-chloropyrazole structure according to claim 1, characterized by the following steps:
3. the use of difluoromethyl pyrazole oxime ester I containing 3-trifluoromethyl-5-chloropyrazole structure according to claim 1 for the preparation of insecticides, wherein: the compound is used alone; or the compound I in claim 1 is used as an active ingredient, and is added with pesticide auxiliary agents commonly used in the field to be processed into an insecticidal composition of an aqueous emulsion, a suspending agent, a water dispersible granule and an emulsifiable concentrate.
4. The use of difluoromethyl pyrazole oxime ester I containing 3-trifluoromethyl-5-chloropyrazole structure according to claim 3 for the preparation of insecticides, wherein: when the compound I is used as an active ingredient of an insecticide, the content in the insecticide may be selected in the range of 0.1% to 99.5%.
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Cited By (2)
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| CN111635399A (en) * | 2020-07-01 | 2020-09-08 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| WO2022002193A1 (en) * | 2020-07-01 | 2022-01-06 | 南通大学 | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
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Cited By (4)
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| CN111635399A (en) * | 2020-07-01 | 2020-09-08 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| WO2022002193A1 (en) * | 2020-07-01 | 2022-01-06 | 南通大学 | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
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| GB2610789A (en) * | 2020-07-01 | 2023-03-15 | Univ Nantong | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
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